KR101202667B1 - Ether-type reactive plasticizer for plstic bonded explosives - Google Patents

Abstract

The present invention relates to an ester-based reactive plasticizer for a composite explosive. More specifically, provided is a high-performance insensitive ester-based reactive plasticizer for a composite explosive having no leakage problem of the plasticizer as combined with a polymer binder used for a composite explosive.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an ether-based reactive plasticizer,

TECHNICAL FIELD The present invention relates to an energizing plasticizer for a complexing medicament, and more particularly, to a high-performance and non-insensitive medicinally energizing medicinal plasticizer that is combined with a polymeric binder used in a complexing agent,

The desensitization of materials with high energy properties is now an important issue in the development of explosives and propellants. As part of this effort, plastic bonded explosives (PBXs) with low sensitivity and improved mechanical properties have been developed while maintaining high energy properties. These PBXs are becoming a fundamental component of high energy charge components, polymeric binders and other small amounts of additives (plasticizers, stabilizers, etc.).

A widely used polymer binder system is a polyurethane-based polymer binder based on hydroxyl-terminated polybutadiene (HTPB), and has been applied with various additives to increase processability, mechanical properties and chemical stability. These polymeric binders exhibit excellent properties for desensitizing high-energy materials, but they are generally low-energy materials, so lowering the overall energy density of the PBX is a problem. Thus, the energy functional groups such as nitro (C-NO _2), nitrate (O-NO _2), knitted suramin (N-NO _2), azido (-N ₃₎ and difluoro-amino (-NF ₂₎ to Research is under way to increase the overall energy density through the development and application of energized binder and energizing plasticizers.

As used herein, the term "energizing functional group" is a generic term generally used in the field of molecular gunpowder. When it is introduced into a molecular gunpowder or plasticizer, it is known that the functional group contributes to increase energy of the whole compound gun. Such as nitro (C-NO ₂ ), nitrate (O-NO ₂ ), nitramine (N-NO ₂ ), azido (-N ₃ ) and difluoroamino (-NF ₂ ) , The term "energized" means that the energy of the entire molecular gunpower is further increased by a method including, for example, introduction of these functional groups.

However, in the case of polymer binders and plasticizers containing these energy functional groups, problems such as low thermal stability, incompatibility with a powder and difficult processing are involved. Therefore, it is important to realize the high performance and dullness of gunpowder at the same time. In particular, when an energy plasticizer is applied, leakage of the energy plasticizer from the plastic composite powder over a long period of time occurs, and as the energy plasticizer leaks, the impact sensitivity of the plastic composite powder increases, the storage stability decreases, And the long-term stability of the plastic composite powder is weakened due to the decrease of physical properties. Therefore, it is important to realize the high performance and dullness of gunpowder at the same time.

When a high energy polymer material capable of simultaneously realizing high performance and dullness is synthesized, it is predicted that a molecular energy agent and a binder can obtain a new energy material having excellent performance and safety.

It is an object of the present invention to provide a reactive energy-imparting plasticizer which can satisfy the high performance and insensitivity required in a next generation explosive, and can prevent various problems associated with leakage of a plasticizer and leakage.

The compounding agent is mainly composed of a prepolymer and a curing agent for forming a molecular gunpowder and a binder, and other components such as a plasticizer are used as needed. The process of injecting all of these components into the target body after making it compatible with each other is referred to as a casting process. After that, the prepolymer and the curing agent react with each other in the body to solidify the components in the body, At this time, the prepolymer and the curing agent react to form a binder.

'Reactive plasticizer' is a low-viscosity, high-energy alkyne compound that can act as a plasticizer in the process of compounding agent mixing. In addition, . The reactive plasticizer is a substance which acts as a plasticizer when preparing a composite explosive and has a property that a part or all of the plasticizer is cured due to the polymerization reaction of the plasticizer during the curing reaction in the final processing step.

When a reactive plasticizer is used in the process of introducing a high energy prepolymer in the process of preparing a compounding agent, the viscosity problem can be solved by acting as a plasticizer in the casting process. In the curing process, a bleeding phenomenon And the migration phenomenon can be reduced, thereby completing the present invention.

That is, the present invention relates to a novel compound having a functional group capable of binding with a side chain of a high-energy polymeric binder by reacting with a corresponding energized prepolymer / curing agent in a curing reaction at the time of preparing a complexing medicinal agent, Reactive energizing plasticizers.

The reactive energizing plasticizers according to the present invention are bonded to side chains of a binder by a click reaction of an azide group and an acetylene group in a curing reaction process and include an acetylene group as a functional group for such bonding, The linkage of < / RTI > Thus, the novel reactive energizing plasticizers according to the present invention can be classified as reactive high energy plasticizers whose type of linkage connected to their backbone is etheric.

The ether-based reactive high-energy plasticizer according to the present invention is an ether-based polymer compound obtained according to the following Reaction Scheme 1:

[Reaction Scheme 1]

(Wherein n is a natural number of 1 to 10).

According to Reaction Scheme 1, a reactive energizing plasticizer containing an ether group in its main chain is synthesized through an acetal formation reaction between 2,2-dinitropropanol (DNP-OH) and an alcohol (AA) containing an acetylene group.

The acetal formation reaction can be carried out under ordinary reaction conditions and is formed by the reaction of an aldehyde and an excess alcohol. Through the competitive reaction of an alcohol containing DNP-OH and an acetylene group, a reactive energizing plasticizer Is synthesized.

The alcohol containing an acetylene group used in the above reaction is, for example, propargyl alcohol when n = 1, 3-butyn-1-ol when n = 2, - ((2,2-dinitropropoxy) methoxy) propane (DNPMPY) or 4 - ((2,2-dinitropropoxy) methoxy) -but- .

Reactive energizing plasticizers are used in the production of plastic composite explosives, while maintaining the essential properties of energy-saving plasticizers required in the process of manufacturing plastic composite explosives, that is, increasing the energy density and improving the processability by decreasing the viscosity of the compounding process. So that it is combined with the polymer binder through the covalent bond with the side chain of the polymer binder in the curing process so that the leakage problem of the existing energy plasticizer can be prevented.

Accordingly, when the reactive energizing plasticizer according to the present invention is applied to the production of a plastic composite explosive, problems caused by leakage of the plasticizer in a plastic composite explosive using a conventional plasticizer are prevented, There is an effect that the energy density is increased in the compounding composition.

1 is a graph showing the results of FT-IR spectrum analysis of DNPMPY.
2 is a graph showing the results of DSC analysis of DNPMPY.
3 is a graph showing FT-IR spectrum results of DNPMBY.
4 is a graph showing viscosity changes of the GAP polyol prepolymer, the synthesized DNPMPY and the mixture thereof (1: 1 weight ratio) measured in Experimental Example 1. Fig.

Production Example 1

Synthesis and Analysis of 3 - ((2,2-dinitropropoxy) methoxy) propane (DNPMPY)

DNPMPY, a reactive energizing plasticizer, was synthesized by acetal formation reaction (Scheme 2).

[Reaction Scheme 2]

(MC), DNP-OH (5 g, 33.56 mmol) and propargyl alcohol (PA) (5.64 g, 100.68 mmol) were injected into a two-necked flask under a nitrogen atmosphere and 1,3,5 -Trioxane (2.21 g, 24.61 mmol, or para-formaldehyde). After the mixture was stirred at 0 ° C for 10 minutes, BF ₃ OEt ₂ (10.48 g, 73.83 mmol) was slowly added dropwise. Then, the reaction temperature was raised to room temperature and reacted for 3 hours. The reaction was poured into 50 mL of distilled water, washed with NaHCO ₃ (10%) solution, and washed twice more with distilled water. The solvent was removed under reduced pressure, and then purified by chromatography (ethyl acetate: hexane = 1: 5) to obtain DNPMPY.

The structure of DNPMPY synthesized was confirmed by the following methods. The structure was first confirmed by ¹ H and ¹³ C NMR and the results were as follows: ¹ H NMR (CDCl ₃ , d, ppm): 2.20 (-CH ₃ ), 2.45 (= CH), 4.20 _{-CH 2 -), 4.30 (-CH} 2 -), 4.75 (-CH 2 -). _{^{13 C NMR (CDCl 3, d}} , ppm): 20.0, 55.5, 69.0, 79.0, 94.5, 117.5.

The results were as follows: (%) Calculated for DNPMPY: C 38.53, H 4.62, N 12.84, O 44.01, Found: C 38.95, H 4.25, N 13.64, O 43.16.

As shown in Fig. 1, FT-IR spectrum confirmed the synthesis of DNPMPY from the functionalized absorption peaks and the results were as follows: IR (cm ^-1 ) 3300 (= CH), 2930 (-C = C-), 1590 ( -NO 2).

The thermal properties of the synthesized reactive energizing plasticizer, DNPMPY, were measured using differential scanning calorimetry (DSC) and the results are shown in FIG. According to DSC results, the synthesis of the reactive plasticizer energizing DNPMPY glass transition temperature (T _g) is a -89 ℃, GAP (glycidyl azide polymer) of about 35 ℃ -55 ℃ than the Tg of the plasticizer, low T _g Respectively.

Production Example 2

Synthesis and Analysis of 4 - ((2,2-dinitropropoxy) methoxy) -but-1-amine) (DNPMBY)

DNPMBY, a reactive energy plasticizer, was synthesized by acetal formation reaction (Scheme 3).

[Reaction Scheme 3]

To the two-necked flask under a nitrogen atmosphere, 30 mL of methylene chloride, DNP-OH (4 g, 26.85 mmol) and 3-butain-1-ol (BO) (5.52 g, 80.55 mmol) , 5-trioxane (1.61 g, 17.9 mmol, or para-formaldehyde). After this mixture was stirred for 10 minutes eseo 0 ℃, the _{BF 3 · OEt 2 (11.44g,} 80.55mmol) was slowly added dropwise. After stirring at 0 ° C for 40 minutes, the reaction temperature was raised to room temperature, and the reaction was allowed to proceed for 5 hours. The reaction was poured into 50 mL of distilled water, washed with NaHCO ₃ (10%) solution, and washed twice more with distilled water. The solvent was removed under reduced pressure, and then purified by chromatography (ethyl acetate: hexane = 1: 7 v: v) to obtain DNPMBY.

The structure of DNPMBY was confirmed by the following methods. The structure was first identified using ¹ H and ¹³ C NMR and the results were as follows: ¹ H NMR (CDCl ₃ , d, ppm): 2.09 (= CH), 2.15 (-CH ₃ ), 2.44 -CH ₂ -), 3.61 (-CH ₂ -O-), 4.35 (-O-CH ₂ -O-), 4.68 (-CH ₂ -O-). _{^{13 C NMR (CDCl 3, d}} , ppm): 20.0, 20.1, 67.1, 69.0, 70.2, 82.1, 96.5, 117.5.

Also, the elemental analysis results for the synthesized DNPMBY were as follows: (%) Calculated for DNPMBY: C 41.38, H 5.21, N 12.06, O 41.35, found C 41.60, H 5.34, N 12.97, O 40.09).

As shown in FIG. 3, the synthesis of DNPMBY was confirmed from the functional group absorption peak from the results of FT-IR spectroscopy. The results were as follows: IR (cm ^-1 ) 3300 (= CH), 2930 2300 (-C = C-), 1590 (-NO 2).

The plasticizers for the preparation of the synthesized complexpowder were mixed with the prepolymer to measure the plasticity of the mixture by measuring viscosity decrease and glass transition temperature drop. The results are shown in the following Experimental Examples.

Experimental Example 1

Reduction of prepolymer viscosity by plasticizer

The viscometer used for the viscosity measurement was an MCR 301 of Anton Paar Physica Co. and a constant plate of 1.0 s ^-1 was measured using a parallel plate (CP25-1-SN9356, diameter = 25 mm) with a 1 mm gap The shear rate was measured at a heating rate of 1 ° C / min in a temperature range of 30 to 60 ° C. After measuring the viscosity of the GAP polyol prepolymer itself, the viscosity of the plasticizer DNPMPY synthesized according to Preparation Example 1 and a mixture thereof (1: 1 weight ratio) was measured to determine the plasticizing property with decreasing viscosity. The results of applying DNPMPY, a plasticizer synthesized according to Preparation Example 1, are shown in FIG. As shown in FIG. 4, the viscosity of the plasticizer / GAP polyol prepolymer mixture synthesized with respect to the viscosity of the GAP polyol prepolymer itself was markedly reduced over the entire measured temperature range, indicating that the plasticizing effect of the synthesized DNPMPY plasticizer was excellent .

The plasticizing effect of viscosity reduction was compared with the currently used energy plasticizers (BDNPF / BDNPA; BDNPF / BDNPDF; BDNPF / BDNBF), and the results are shown in Table 1 below. The viscosity was measured under the same conditions as in this experiment. For reference, the viscosity of the GAP polyol prepolymer itself is 6,015 cP at 30 占 폚 and 1,035.5 cP at 60 占 폚.

The viscosity of the GAP polyol prepolymer / plasticizer (1/1 w / w) mixture at 30 < 0 > C and 60 & Furtherance
(1: 1 weight ratio) Viscosity (cP) 30 ℃ 60 ° C GAP: DNPMPY 931 227 GAP: BDNPF / BDNPA 1,441 295 GAP: BDNPF / BDNPDF 1,211 197 GAP: BDNPF / BDNBF 1,351 274

BDNPF: Bis (2,2-dinitropropyl) formal (bis (2,2-dinitropropyl)

BDNPA: Bis (2,2-dinitropropyl) acetal bis (2,2-dinitropropyl)

BDNPDF: Bis (2,2-dinitropropyl) diformal bis (2,2-dinitropropyl)

BDNBF: Bis (2,2-dinitrobutyl) formal)

According to Table 1, it can be confirmed that the DNPMPY plasticizer synthesized according to the present invention is excellent in the viscosity reduction effect on the GAP polyol prepolymer.

Claims (2)

An ether compound used in a plasticizer for preparing a composite explosive having the following formula:

(Wherein n is a natural number of 1 to 10). The compound according to claim 1, wherein the compound is prepared by an acetal-forming reaction of 2,2-dinitropropanol with an acetylene group-containing alcohol.

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